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US6893736B2 - Thermosetting resin compositions useful as underfill sealants - Google Patents

Thermosetting resin compositions useful as underfill sealants Download PDF

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US6893736B2
US6893736B2 US10/294,668 US29466802A US6893736B2 US 6893736 B2 US6893736 B2 US 6893736B2 US 29466802 A US29466802 A US 29466802A US 6893736 B2 US6893736 B2 US 6893736B2
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epoxy resin
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methylimidazole
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US20030131937A1 (en
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Mark M. Konarski
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Henkel IP and Holding GmbH
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the groups H01L21/18 - H01L21/326 or H10D48/04 - H10D48/07 e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0102—Calcium [Ca]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01025—Manganese [Mn]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01046—Palladium [Pd]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01078—Platinum [Pt]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12528—Semiconductor component

Definitions

  • thermosetting resin compositions useful as underfill sealants for mounting to a circuit board semiconductor chips or semiconductor device packages, which have a semiconductor chip on a carrier substrate.
  • Reaction products of these compositions demonstrate improved adhesion after exposure to elevated temperature conditions, improved resistance to moisture absorption and improved resistance to stress cracking.
  • curable resin compositions generally are known. See e.g., U.S. Pat. No. 4,645,803 (Kohli), which relates to curable epoxy resin compositions of reinforcing filaments and epoxy resins together with a primary amine-functional curing agent with or without a polyamine curing agent and a curing catalyst which when cured into a fiber matrix is useful in preparing composites and prepreg materials for structural applications.
  • U.S. Pat. No. 4,499,245 (Ikeguchi) relates to a curable resin composition requiring a mixture and/or a reaction product of (a) a polyfunctional dicyandiamide, prepolymer of the dicyandiamide or coprepolymer of the dicyandiamide and an amine and (b) a polyhydantion resin—a phenolic-based epoxy curative.
  • a polyfunctional maleimide, prepolymer of the maleimide or coprepolymer of the maleimide and an amine may be included as a component (c).
  • thermosetting compositions of dicyandiamides and epoxy resins are also generally known. See e.g., Japanese patent document JP 62-275,123, an English-language abstract of which speaks to a resin composition for preparing prepreg materials with reinforcing fiber for structural applications.
  • the compositions are reported to include certain dicyandiamides, bismaleimide, polyether sulfone (as a non-reactive thermoplast whose use is as a toughening agent) and bisphenol F- or A-type epoxy resin.
  • the composition is reported to be optionally hardened by a hardening catalyst, one of which is noted as imidazole.
  • U.S. Pat. No. 4,918,157 (Gardner) relates to the use of urea compounds as latent cure accelerators for dicyandiamides, and to thermosetting dicyandiamide formulations of dicyandiamides and urea compounds. More specifically, the '157 patent claims a thermosetting composition of a dicyandiamide; a urea compound selected from alkyl aryl ureas, aryl ureas and mixtures thereof; and an epoxy resin.
  • the curable dicyandiamide formulations of the '157 patent are reportedly useful as matrix resins, and for the production of prepreg, fiber-reinforced laminates, composites and the like.
  • Epoxy curing systems are also known. See e.g., U.S. Pat. No. 3,862,260 (Sellers), in which a curing agent of a trifunctional hardener (such as the reaction product of one mole of bisphenol A with one mole of formaldehyde) and an imidazole is disclosed.
  • a curing agent of a trifunctional hardener such as the reaction product of one mole of bisphenol A with one mole of formaldehyde
  • an imidazole is disclosed.
  • thermosetting resin compositions appear to be directed to structural applications, as contrasted to the microelectronic application to which the compositions of the present invention are directed.
  • the use of epoxy resin compositions as matrix compositions for fiber reinforcement in prepreg, composite and laminate materials for structural materials differs significantly from the use of epoxy resin compositions as an adhesive and encapsulant in microelectronic applications, such as with electrical solder junctions in semiconductor chips, and creates different demands and requirements from the uncured resin as well as cured reaction products thereof.
  • the resins begin to cure upon introduction of the curing agent or catalyst. This causes viscosity increases which leads to reduced dispensability. While such viscosity increase may be alleviated to some degree by using a liquid curing agent or catalyst, liquid catalysts tend to decrease latency to a point which is not commercially practical with current production demands. And introduction of a solid catalyst, such as imidazole, has limited applicability because its presence often changes the rheological properties of the composition, and decreases flow.
  • an underfilling sealant composition to provide good adhesive properties while flowing and curing in a reasonable time to be commercially appealing and possessing an extended useful working life.
  • the present invention provides a thermosetting resin composition useful as an underfilling sealant composition which (1) fills the underfill space in a semiconductor device, such as a FC assembly which includes a semiconductor chip mounted on a carrier substrate or a CSP, which includes a semiconductor chip mounted on a carrier substrate, (2) enables the semiconductor to be securely connected to a circuit board by short-time heat curing and with good productivity, (3) demonstrates excellent heat shock properties (or thermal cycle properties), and (4) provides a composition that does not begin to cure at conventional underfill dispensing temperatures and exhibits commercially desirable flow properties, even when highly filled with an inorganic filler, such as at or above a 75 weight percent filler loading level.
  • a semiconductor device such as a FC assembly which includes a semiconductor chip mounted on a carrier substrate or a CSP, which includes a semiconductor chip mounted on a carrier substrate
  • enables the semiconductor to be securely connected to a circuit board by short-time heat curing and with good productivity (3) demonstrates excellent heat shock properties (or thermal cycle properties)
  • (4) provides a
  • thermosetting resin compositions of this invention which are used as underfill sealants between such a semiconductor device and a circuit board to which the semiconductor device is electrically connected, include an epoxy resin component, a latent hardener component and a polysulfide-based toughening component.
  • the latent hardener component includes a modified amide component, such as dicyandiamide, a latent catalyst therefor, such as an imidazole, a diazabicycloundecaene (“DBU”) salt, a tertiary amine salt, and/or a modified urea.
  • the latent catalyst is an imidazole, particularly one in the solid state.
  • thermosetting resin compositions of this invention semiconductor devices, such as flip chip assemblies, may be (1) assembled quickly and without production line down time because of improved cure speed and extended useful working life, and (2) securely connected to a circuit board by short-time heat curing of the composition, with the resulting mounted structure (at least in part due to the cured composition) demonstrating excellent heat shock properties (or thermal cycle properties).
  • compositions of this invention may also be used for microelectronic applications beyond sealing underfill, such as with glob top, die attachment and other applications for thermosetting compositions in which high filler loadings and an extended useful working life are desirable.
  • FIG. 1 depicts a cross-sectional view showing an example of a mounted structure with which the thermosetting resin composition of the present invention is used as an underfill sealant.
  • thermosetting resin compositions which are useful as underfill sealants between a semiconductor device and a circuit board to which the semiconductor device is electrically connected, include an epoxy resin component, a latent hardener component and a polysulfide-based toughening component.
  • the latent hardener component includes a modified amide component, such as dicyandiamide, a latent catalyst, such as an imidazole, a DBU salt, a tertiary amine salt, and/or a modified urea.
  • the latent catalyst is an imidazole, particularly one in the solid state.
  • the inventive composition includes a filler, desirably at least a portion of the filler should have a particle size in the range of 1 to 1,000 nanometers.
  • an unfilled inventive composition includes about 100 parts by weight of the epoxy resin component; 0 to about 30 parts by weight, such as about 5 to about 25 parts, dersirably about 10 parts, of the latent hardener component, of which 0 to about 15 parts, such as about 5 to about 10 parts, desirably 7 parts, is comprised of the modified amide component, such as dicyandiamide and 0 to about 15 parts, such as about 1 to about 5 parts, such as about 3 parts, is comprised of the latent catalyst therefor, such as an imidazole, a DBU salt, a tertiary amine, and/or a modified urea; and 0 to about 30 parts, such as about 5 to about 25 parts, desirably about 10 parts, of the polysulfide-based toughening component.
  • the modified amide component such as dicyandiamide
  • the latent catalyst therefor such as an imidazole, a DBU salt, a tertiary amine, and/or
  • the epoxy resin component of the present invention may include any common epoxy resin.
  • This epoxy resin may be comprised of at least one multifunctional epoxy resin, optionally, together with at least one monofunctional epoxy resin.
  • the multifunctional epoxy resin should be included in amount within the range of about 20 parts to about 100 parts of the epoxy resin component.
  • the amount thereof should be in the range of from about 40 to 80 parts.
  • a monofunctional epoxy resin if present, should ordinarily be used as a reactive diluent, or crosslink density modifier. In the event such a monofunctional epoxy resin is included as a portion of the epoxy resin component, such resin should be employed in an amount of up to about 20% by weight based on the total epoxy resin component.
  • the monofunctional epoxy resin should have an epoxy group with an alkyl group of about 6 to about 28 carbon atoms, examples of which include C 6 -C 28 alkyl glycidyl ethers, C 6 -C 28 fatty acid glycidyl esters and C 6 -C 28 alkylphenol glycidyl ethers.
  • Such epoxy resin(s) include generally, but are not limited to, polyglycidyl ethers of polyvalent phenols, for example pyrocatechol; resorcinol; hydroquinone; 4,4′-dihydroxydiphenyl methane; 4,4′-dihydroxy-3,3′-dimethyldiphenyl methane; 4,4′-dihydroxydiphenyl dimethyl methane; 4,4′-dihydroxydiphenyl methyl methane; 4,4′-dihydroxydiphenyl cyclohexane; 4,4′-dihydroxy-3,3′-dimethyldiphenyl propane; 4,4′-dihydroxydiphenyl sulfone; tris(4-hydroxyphyenyl)methane; polyglycidyl ethers of the chlorination and bromination products of the above-mentioned diphenols; polyglycidyl ethers of novolacs (i.e., reaction products of monohydric or polyhydr
  • reactive diluents from CVC Chemicals include o-cresyl glycidyl ether (GE-10), p-t-butyl phenyl glycidyl ether (GE-11), neopentyl glycol di-glycidyl ether (GE-20), 1,4-butanediol di-glycidyl ether (GE-21), and cyclohexanedimethanol glycidyl ether (GE-22).
  • Other reactive diluents available commercially from CVC include castor oil tri-glycidyl ether (GE-35) and propoxylated glycerin tri-glycidyl ether (GE-36).
  • epoxy compounds include polyepoxy compounds based on aromatic amines and epichlorohydrin, such as N,N′-diglycidyl-aniline; N,N′-dimethyl-N,N′-diglycidyl-4,4′-diaminodiphenyl methane; N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenyl methane; N-diglycidyl-4-aminophenyl glycidyl ether; and N,N,N′,N′-tetraglycidyl-1,3-propylene bis-4-aminobenzoate.
  • polyepoxy compounds based on aromatic amines and epichlorohydrin such as N,N′-diglycidyl-aniline; N,N′-dimethyl-N,N′-diglycidyl-4,4′-diaminodiphenyl methane; N,N,N′,N′-
  • multifunctional epoxy resin examples include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, and cresol novolac-type epoxy resin.
  • epoxy resins suitable for use herein are polyglycidyl derivatives of phenolic compounds, such as those available commercially under the tradenames EPON 828, EPON 1001, EPON 1009, and EPON 1031, from Shell Chemical Co.; DER 331, DER 332, DER 334, and DER 542 from Dow Chemical Co.; RE-310-S, RE-404-S and BREN-S from Nippon Kayaku, Japan.
  • Other suitable epoxy resins include polyepoxides prepared from polyols and the like and polyglycidyl derivatives of phenol-formaldehyde novolacs, the latter of which are available commercially under the tradenames DEN 431, DEN 438, and DEN 439 from Dow Chemical Company.
  • Cresol analogs are also available commercially ECN 1235, ECN 1273, and ECN 1299 from Vantico, Inc.
  • SU-8 is a bisphenol A-type epoxy novolac available from Interez, Inc.
  • Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also useful in this invention, commercially available resins of which include GLYAMINE 135, GLYAMINE 125, and GLYAMINE 115 from F.I.C.
  • the latent hardener includes a modified amide and a latent catalyst therefor.
  • the modified amide such as the cyano-functionalized amide dicyandiamide or cyanoguanidine (available commercially as CG-1400 or CG-1600 from Air Products), may be included in an amount up to about 5 weight percent, such as about 1 to about 2 weight percent, based on the total composition.
  • the latent catalyst for the modified amide includes imidazoles, such as imidazole and derivatives thereof, such as isoimidazole, imidazole, alkyl substituted imidazoles, such as 2-methyl imidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, butylimidazole, 2-heptadecenyl-4-methylimidazole, 2-methylimidazole, 2-undecenylimidazole, 1-vinyl-2-methylimidazole, 2-n-heptadecylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-ethyl 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl
  • Particulary desirable latent catalysts include DBU-phenolate, available commercially from Air Products under the tradename SA1, DBU-hexanoate available commercially from Air Products under the tradename SA102, DBU-formate available commercially from, Air Products under the tradename SA610, and DBU-p-toluenesulfonate available commercially from Air Products under the tradename SA501.
  • Still other latent catalysts include phenyldimethyl urea, available commercially from CVC under the tradename U-405, toluene bis(dimethyl urea) available commercially from CVC under the tradename U-410, and methylene diphenyl bis(dimethyl urea), available commercially from CVC under the tradename U415.
  • Tertiary amine salts are also desirable.
  • polysulfide-based toughening component many materials may be used.
  • a polysulfide-based toughening components of the general formulae may be used:
  • THIOKOL LP-3 A particularly desirable material is known as THIOKOL LP-3, available commercially from Rohm and Haas Company, Philadelphia, Pa., where n is 6 and about 2 mole percent branching exists. LP-3 is also reported to have a molecular weight of about 1,000.
  • Another particularly desirable material is avaliable commericially from Akcros Chemicals, Manchester, Great Britain under the tradename THIOPLAST, such as G1 (n is 19-21, 1.8-2 percent thiol content, and a 3,300-3,700 molecular weight), G4 (n is less than 7, less than 5.9 percent thiol content, and less than 1,100 molecular weight), G12 (n is 23-26, 1.5-1.7 percent thiol content, and a 3,900-4,400 molecular weight), G21 (n is 12-15, 2.5-3.1 percent thiol content, and a 2,100-2,600 molecular weight), G22 (n is 14-18, 2.1-2.7 percent thiol content, and a 2,400-3,100 molecular weight), G112 (n is 23-25, 1.5-1.7 percent thiol content, and a 3,900-4,300 molecular weight), and G131 (n is 30-38, 1.5-1.7 percent thiol content, and a 5,000-6,500 molecular weight).
  • thermosetting resin compositions according to the present invention penetrate and flow readily into the space between the circuit board and the semiconductor device, or at least show a reduction in viscosity under heated or use conditions thus penetrating and flowing easily.
  • thermosetting resin compositions of this invention by selecting the types and proportions of various so that the gel times will be tailored to a specified period of time (such as about 5 minutes or 6 minutes) at a temperature of about 165° C.
  • the inventive compositions should show no or substantially no increase of viscosity after a period of time of about 30 minutes at underflow temperatures of about 90 to about 130° C.
  • the compositions penetrate into the space between the circuit board and the semiconductor device (e.g., of 50 to 200 ⁇ m) relatively uniformly, and allow for an assembly of greater size to be filled without observing a viscosity increase in the composition thereby rendering it less effective for application.
  • thermosetting resin composition of the present invention may further contain other additives such as transition metal complexes as catalysts, defoaming agents, leveling agents, dyes, pigments and fillers.
  • the compositions may also contain photopolymerization initiators, provided such materials do not adversely affect the desired properties of the composition.
  • the transition metal complex may be chosen from a variety of organometallic materials or metallocenes. Those materials of particular interest herein may be represented by metallocenes within structure I: where R 1 and R 2 may be the same or different and may occur at least once and up to as many four times on each ring in the event of a five-membered ring and up to as many as five times on each ring in the event of a six-membered ring;
  • the element represented by M e may have additional ligands—Y 1 and Y 2 —associated therewith beyond the carbocyclic ligands depicted above (such as where M e is Ti and Y 1 and Y 2 are Cl ⁇ ).
  • metallocene structure I may be modified to include materials such as those within structure II below: where R 1 , R 2 , Y 1 , Y 2 , A, A′, m, m′ and M e are as defined above.
  • R 1 and R 2 are each H; Y 1 and Y 2 are each Cl; A and A′ are each N; m and m′ are each 2 and M e is Ru.
  • metallocene structure I well-suited metallocene materials may be chosen from within metallocene structure III: where R 1 , R 2 and M e are as defined above.
  • Particularly well-suited metallocene materials from within structure I may be chosen where R 1 , R 2 , Y 1 , Y 2 , m and m′ are as defined above, and M e is chosen from Ti, Cr, Cu, Mn, Ag, Zr, Hf, Nb, V and Mo.
  • the metallocene is selected from ferrocenes (i.e., where M e is Fe), such as ferrocene, vinyl ferrocenes, ferrocene derivatives, such as butyl ferrocenes or diarylphosphino metal-complexed ferrocenes [e.g., 1,1-bis (diphenylphosphino) ferrocene-palladium dichloride], titanocenes (i.e., where M e is Ti), such as bis(n 5 -2,4-cyclopentadien-1-yl)-bis-[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl] titanium which is available commercially from Ciba Specialty Chemicals, Tarrytown, N.Y. under the tradename “IRGACURE” 784DC, and derivatives and combinations thereof.
  • M e ferrocenes
  • M e is Fe
  • ferrocene i
  • bis-alkylmetallocenes for instance, bis-alkylferrocenes (such as diferrocenyl ethane, propanes, butanes and the like) are also desirable for use herein, particularly since about half of the equivalent weight of the material (as compared to a non-bis-metallocene) may be employed to obtain the sought-after results, all else being unchanged.
  • bis-alkylferrocenes such as diferrocenyl ethane, propanes, butanes and the like
  • propanes propanes, butanes and the like
  • M e [CW 3 —CO—CH ⁇ C(O ⁇ )—CW′ 3 ] 2
  • W and W′ may be the same or different and may be selected from H, and halogens, such as F and Cl.
  • Examples of such materials include platinum (II) acetylacetonate (“PtACAC”), cobalt (II) acetylacetonate (“Co(II)ACAC”), cobalt (III) acetylacetonate (“Co(III)ACAC”), nickel (II) acetylacetonate (“NiACAC”), iron (II) acetylacetonate (“Fe(II)ACAC”), iron (III) acetylacetonate (“Fe(III)ACAC”), chromium (II) acetylacetonate (“Cr(II)ACAC”), chromium (III) acetylacetonate (“Cr(III)ACAC”), manganese (II) acetylacetonate (“Mn(II)ACAC”), manganese (III) acetylacetonate (“Mn(III)ACAC”) and copper (II) acetylacetonate
  • thermosetting compositions in addition to the epoxy resin component and latent hardener component, include a filler component.
  • the filler component acts to lower moisture pick up, and tends to increase viscosity.
  • Appropriate filler components include silica, alumina, silica-coated aluminum nitride, silver flake and the like.
  • the filler desirably acts to better match the coefficient of thermal expansion (“CTE”) of the substrates with which the inventive compostions are intended to be used.
  • CTE coefficient of thermal expansion
  • the particle size of the filler is desirably in the range of about 0.1-10 microns, such as on the order of about 2 microns.
  • a silica filler having such a particle size is commercially available from Admatechs, Japan under the tradename ADMAFINE, such as ADMAFINE designations SO—C1 (average paricle size, 0.2 microns); SO—C2 (average paricle size, 0.4-0.6 microns); SO—C3 (average paricle size, 0.8-1.2 microns); SO—C5 (average paricle size, 1.5-2.0 microns); SO-E1 (average paricle size, 0.2 microns); SO-E2 (average paricle size, 0.4-0.6 microns); SO-E3 (average paricle size, 0.8-1.2 microns); and SO-E5 (average paricle size, 1.5-2.0 microns).
  • the SO-E versions have low iron ( ⁇ 2 ppm), low aluminum (6 ppm), low calcium ( ⁇ 2
  • silica filler with such particle size range is Tokuyama Corporation, Yamaguchi, Japan, which makes available commercially under the tradename EXCELICA, grades SE-8 (average particle size, 7.9 microns—particle size distribution: more than 150 microns, ⁇ 0.001%; 106-150 microns, ⁇ 0.01%; 75-106 microns, 0.0%; 45-75 microns, 0.2%; and less than 45 microns, 99.8%); SE-5 (average particle size, 5.1 microns—particle size distribution: more than 150 microns, ⁇ 0.001%; 106-150 microns, ⁇ 0.01%; 75-106 microns, 0.0%; 45-75 microns, 0.1%; and less than 45 microns, 99.9%); SE-3B (average particle size, 3.0 microns—particle size distribution: more than 20 microns, ⁇ 0.1%); and SE-1 (average particle size, 1.9 microns).
  • the filler component may include filler particles in the 1-1,000 nanometer (“nm”) range.
  • a commercially available example of such filler particles is sold under the tradename NANOPOX, such as NANOPOX XP 22, by Hans Chemie, Germany.
  • NANOPOX fillers are monodisperse silica filler dispersions in epoxy resins, at a level of up to about 50% by weight.
  • NANOPOX fillers ordinarily are believed to have a particle size of about 5 nm to about 80 nm.
  • NANOPOX XP 22 is reported to contain 40 weight percent of silica particles having a particle size of about 15 nm in the diglycidyl ether of bisphenol-F epoxy resin.
  • inorganic filler component includes those constructed of or containing aluminum oxide, silicon nitride, aluminum nitride, silica-coated aluminum nitride, boron nitride and combinations thereof.
  • the inorganic filler component should be used in an amount of about 10 to about 80 percent by weight of the compostion, such as about 25 to about 75 percent by weight, desirably within the range of about 35 to about 70 percent by weight.
  • FIG. 1 shows a mounted structure (i.e., a flip chip package) in which a thermosetting resin composition of the present invention has been applied and cured.
  • the flip chip package 4 is formed by connecting a semiconductor chip (a bare chip) 2 to a carrier substrate 1 (e.g., a circuit board) and sealing the space therebetween suitably with a thermosetting resin composition 3 .
  • This semiconductor device is mounted at a predetermined position on the carrier substrate 1 , and electrodes 5 and 6 are electrically connected by a suitable electrical connection means 7 and 8 , such as solder.
  • a suitable electrical connection means 7 and 8 such as solder.
  • the space between the semiconductor chip 2 and the carrier substrate 1 is sealed with the inventive thermosetting resin composition 3 , and then cured.
  • the cured product of the thermosetting resin composition should completely fill that space.
  • Carrier substrates may be constructed from ceramic substrates of Al 2 O 3 , SiN 3 and mullite (Al 2 O 3 —SiO 2 ); substrates or tapes of heat-resistant resins, such as polyimides; glass-reinforced epoxy; ABS and phenolic substrates which are also used commonly as circuit boards; and the like. Any electrical connection of the semiconductor chip to the carrier substrate may be used, such as connection by a high-melting solder or electrically (or anisotropically) conductive adhesive, wire bonding, and the like. In order to facilitate connections, the electrodes may be formed as bumps.
  • the resulting structure is ordinarily subjected to a continuity test or the like. After passing such test, the semiconductor chip may be fixed thereto with a thermosetting resin composition, as described below. In this way, in the event of a failure, the semiconductor chip may be removed before it is fixed to the carrier substrate with the thermosetting resin composition.
  • thermosetting resin composition in accordance with this invention is applied to the periphery of the electronically-connected semiconductor chip.
  • the composition penetrates by capillary action into the space between the carrier substrate and the semiconductor chip.
  • thermosetting resin composition is then thermally cured by the application of heat.
  • the thermosetting resin composition shows a significant reduction in viscosity and hence an increase in fluidity, so that it more easily penetrates into the space between the carrier substrate and the semiconductor chip.
  • the thermosetting resin composition is allowed to penetrate fully into the entire space between the carrier substrate and the semiconductor chip.
  • thermosetting resin compositions of the present invention demonstrate excellent adhesive force, heat resistance and electric properties, and acceptable mechanical properties, such as flex-cracking resistance, chemical resistance, moisture resistance and the like, for the applications for which they are used herein.
  • thermosetting resin composition applied should be suitably adjusted so as to fill the space between the carrier substrate and the semiconductor chip, which amount of course may vary depending on application.
  • Thermosetting resin compositions of the present invention may ordinarily be cured by heating to a temperature in the range of about 140° C. to about 180° C. for a period of time of about 30 minutes to about 2 hours. However, generally after application of the composition, an initial cure time of about 10 minutes sets up the composition, and complete cure is observed after about 90 minutes at about 165° C. Thus, the composition of the present invention can be at moderately high temperatures and with long underfilling times which are necessary to achieve very low CTEs with high filler loadings and large sized dice.
  • compositions in accordance with the present invention were prepared and evaluated for performance in contrast with compositions prepared without the dicyandiamide component or the latent hardener component.
  • the compositions are set forth in Table 1.
  • Performance is evaluated in terms of capillary flow distance of the liquid composition and glass transition temperature (“Tg”) of the cured composition, results for which are set forth in Table 2.
  • compositions A and B illustrate the benefits of including a modified amide, such as dicyandiamide.
  • a modified amide such as dicyandiamide.
  • the inclusion of this component permits the composition to penetrate small gaps for long distances (>60 mm), while maintaining good Tg values and high filler loadings.
  • Composition C has a significantly shorter flow distance even at a lower filler loading, and Composition D has a low Tg value, making it unattractive for many end use applications.
  • compositions were prepared and evaluated without the polysulfide-based toughening component.
  • the composition componets are listed in Table 3. Performance is evaluated in terms of flow distance, moisture absorption and fracture toughenss (K 1 C), the results of which are shown in Table 4.
  • composition E The use of the polysulfide-based toughener, LP-3, in Composition E demonstrates a desirable balance of high flow behaviour and toughness.
  • conventional tougheners such as a CTBN toughener (Composition G) and on acrylate rubber toughener (Composition H)
  • Composition G and H demonstrate significantly moisture uptake, which is seen as detrimental.
  • compositions were prepared with a solid imidazole and a liquid imidazole, and evaluated for performance.
  • the compositions are set forth in Table 5.
  • compositions I and J illustrate the benefits of including a solid imidazole over a liquid imidazole (Composition K) or no latent curative at all (Composition J).
  • Compositions I and J have high Tg values and penetrate small gaps for long distances.

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